Process for the preparation of organochlorostannanes

ABSTRACT

1. A PROCESS FOR THE PRODUCTION OF A CHLOROSTANNANE HAVING THE GENERAL FORMULA:   Z-SN(-Y)(-CL)2   WHEREIN Y IS A CHLORINE ATOM OR A SATURATED OR UNSATURATED ALIPHATIC, CYCLOALIPHATIC OR AROMATIC HYDROCARBON RADICAL, AND Z IS EITHER A GROUP Z1 HAVING THE GENERAL FORMULA:   (R)N-PHENYLENE-   IN WHICH R REPRESENTS A CHLORINE ATOM OR AN ALKYL RADICAL WITH 1 TO 4 CARBON ATOMS AND WHEREIN N IS 0, 1. OR 2, OR A GROUP Z2 HAVING THE GENERAL FORMULA:   R1-C(-R2)=C(-R3)-   IN WHICH R1, R2, AND R3 WHICH MAY BE IDENTICAL OR DIFFERENT, EACH REPRESENTS A HYDROGEN ATOM OR A SATURATED OR UNSATURATED ALIPHATIC, CYCLOALIPHATIC OR AROMATIC HYDROCARBON RADICAL, OR TWO RADICAL R1 AND R3 TOGETHER WITH THE TWO ETHYLENTIC CARBONS TO WHICH THEY AR BONDED, FORM AN UNSATURATED RING HAVING 5 OR 6 CARBON ATOMS IN THE RING, IN WHICH A TIN HALIDE OF THE GENERAL FORMULA:   Y-SN-CL3 II   IS REACTED IN THE PRESENCE OF ALUMINUM CHLORIDE, WITH AN ORGANOSILICON COMPOUND OF THE FORMULA:   (Z)A-SI(-CL)B(-CH3)(4-(A+B))   WHEREIN Y AND Z ARE AS DEFINED ABOVE, A IS 1, 2, 3 OR 5, B IS 0, 1, 2 2 OR 3, THE SUM (A+B) IS NOT GREATER THAN 4, B BEING 0 WHEN Z IS Z2.

United States Patent 3,839,382 PROCESS FOR THE PREPARATION OFORGANOCHLOROSTANNANES Georges Bakassian, St.-Foy-les-Lyon, Michel Gay,Lyon,

and Marcel Lefort, Caluire, France, assignors to Rhone- Poulenc S.A.,Paris, France No Drawing. Filed Aug. 10, 1973, Ser. No. 387,508 Claimspriority, application France, Aug. 11, 1972, 7229099, 7229100 Int. Cl.C07j 7/22 U.S. Cl. 260-4293 7 Claims ABSTRACT OF THE DISCLOSURE Thepresent invention relates to a process for the preparation oforganochlorostannanes containing alkenyl and/ or aromatic groupsdirectly bonded to the tin atom. These organostannanes are produced inaccordance with the process which employs a redistribution reactionbetween tin halides and organosilicon compounds.

Various processes for the production of halogenostannanes possessingalkenyl groups, for example, vinyland allyl-halogenostannanes, are knownat the present time. It is thus possible to prepare diallyl-tindibromide by direct synthesis starting from allyl bromide and finelydivided tin [.l. Org. Chem., 26, 2301 (1961)]. Direct synthesis is not,however, a general process for the production ofalkenylhalogenostannanes, since it appears that it can be carried outonly by using very active alkenyl halides. The most common method forthe preparation of alkenylchlorostannanes such as vinylorallyl-chlorostannanes, involves a redistribution reaction oftetraalkenylstannanes, usually produced by the method employing amagnesium compound, with tetrahalogeno-tin compounds ortrihalogenoorgano-tin compounds (US. Pat. 2,873,288).

Various processes for the production of stannanes possessing aromaticgroups, for example phenylstannanes, are also known. The latter areprepared industrially by direct synthesis by heating aryl halides withfinely divided particles of tin, generally in the presence of activatorssuch as metal iodides. Such processes are described, for example, inFrench Patent Nos. 1,456,268 and 1,087,051. It is also known to preparephenylchlorostannanes by a redistribution reaction starting fromtetraphenyl-tin and tetrachloro-tin or trichloroorgano-tin [BritishPatent 1,070,942 and J. Org. Chem. 1119, 33 (1968)].

Thepresent invention provides a process for the production of achlorostannane having the general formula:

wherein Y is a chlorine atom or a saturated or unsaturated aliphatic,cycloaliphatic or aromatic hydrocarbon radical, and Z is either a groupZ having the general formula:

3,839,382 Patented Oct. 1, 1974 ice in which R represents a chlorineatom or an alkyl radical with 1 to 4 carbon atoms and wherein n is 0, 1or 2, or a group Z having the general formula:

in which R R and R which may be identical or different, each represent ahydrogen atom or a saturated or unsaturated aliphatic, cycloaliphatic oraromatic hydrocarbon radical, or two radicals R and R together with thetwo ethylenic carbons to which they are bonded, form an unsaturated ringhaving 5 or 6 carbon atoms in the ring, in which a tin halide of thegeneral formula:

YSn-Cla is reacted, in the presence of aluminium chloride with anorganosilicon compound of the formula:

z.,si

3)[4-(B+b)l H wherein Y and Z are as defined above, a is 1, 2, 3 or 4, bis O, 1, 2, or 3, the sum (a-l-b) is not greater than 4, b being 0 whenZ is Z Without wishing to prejudge the mechanism of the reaction, webelieve at the moment that it can be represented by the followingequation:

More particularly, when Z=Z n is preferably zero or equal to 1, and whenn is equal to 1, the symbol R represents a chlorine atom or a methylradical. When Z=Z a is preferentially equal to 1 and R R and Rpreferentially represent hydrogen atoms, straight or branched, saturatedor unsaturated, aliphatic hydrocarbon radicals having at most 6 carbonatoms, cycloalkyl or cycloalkenyl radicals possessing 4 to 6 carbonatoms in the ring, or phenyl, alkylphenyl or phenylalkyl radicals inwhich the alkyl group contains 1 to 4 carbon atoms.

Y preferentially represents a chlorine atom, a straight or branched,saturated or unsaturated, aliphatic hydrocarbon radical having at most 6carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl,vinyl and allyl radicals, a cycloalkyl or cycloalkenyl radicalpossessing 4 to 6 carbon atoms in the ring, or a pheny, alkylphenyl orphenylalkyl radical in which the alkyl group contains 1 to 4 carbonatoms.

Amongst the organosilicon compounds which can be used in the processaccording to the invention, there may be mentioned by way ofillustration, amongst the compounds in which Z is represented by Zdivinyldimethylsilane, 1-propenyl-trimethylsilane,1-isopropenyl-trimethylsilane, 1-butenyl-trimethylsilane,(Z-methyl-but-l-enyl)-trimethy1silane,

( 1-methyl-pent-1-enyl -trimethylsilane,

( l-dimethyl-butl-enyl) -trimethylsilane,

1,2- or 2,2-diphenyl-vinyltrimethylsilane and1-methyl-4-phenyl-butl-enyl -trimethylsilane.

Amongst the organosilicon compounds which can be used in the processaccording to the invention, there may me mentioned by way ofillustration, amongst the compounds in which Z is represented by Zphenylthichlorosilane, p-ehlorophenyltrichlorosilane,diphenyldichlorosilane, phenylmethylchlorosilane, phenyltrimethylsilane,phenylmethyldichlorosilane, triphenylchlorosilane, tetraphenylsilane,phenylbenzyldichlorosilane, p-tolylmethyldichlorosilane,bis-p-tolyldichlorosilane, bis-p-tolylmethylchlorosilane and the like.

Amongst the chloro-tin compounds of the formula (II) which can be usedin the process according to the invention, there may be mentioned by wayof illustration, tetrachloro-tin, phenylthichloro-tin,vinyltrichloro-tin, butyltrichloro-tin, octyltrichloro-tin,cyclohexyltrichloro-tin or benzyltrichloro-tin.

Aluminium chloride, which is the catalyst for the redistributionreaction of the present process, can be used in proportions by weightranging from 0.1 to 10% and preferably from 0.5 to relative to the totalweight of the compounds employed. The reaction can optionally be carriedout in a solvent which is inert with respect to reagents and to thereaction products. Benzene, toluene, hexane or cyclohexane may bementioned, by way of illustration, amongst the solvents which can beused.

The organosilicon compound (HI) and the tin halide (II) can be reactedin any proportions whatsoever. In general, a slight excess of theorganosilicon compound relative to the stoichiometric requirements ofthe reaction, as defined above, is added. The reagents, the catalystand, where appropriate, the solvent, are heated in the liquid phase at atemperature which is generally between and 250 C. and preferably between20 and 200 C. The order in which the reagents are employed is notcritical. In general, all of the reagents are heated at the desiredtemperature until the reaction is complete; it is also possible tointroduce the silicon-containing compound gradually into the vesselwhich already contains tetrachloro-tin (or the organo-trichloro-tincompound) and aluminium chloride. It is also possible to remove thevolatile products formed during the reaction, as they are produced. Thereaction can be carried out at a pressure less than, equal to or greaterthan atmospheric pressure.

At the end of the period of heating, the constituents of the reactionmixture can be separated by any known method, for example, by fractionaldistillation. In order to prevent the aluminium chloride from beingcarried away in the distillates and to prevent subsequent side reactionsfrom taking place, it is possible optionally to complex the catalyst inthe final mixture. This operation can be carried out by adding a ketonesuch as acetone, for example, at a temperature of the order of 20 to 25C. It is also possible to add an alkali metal halide, such as so diumchloride, to the final mixture and to heat the mixture for a short time.

The process according to the invention makes it possible to obtainnumerous phenylchlorostannanes and alkenylchlorostannanes. Amongst thephenylchlorostannanes, there may be mentioned by way of illustration,phenyltrichloro-tin, pchlorophenyltrichloro-tin, p-, moro-methylphenyltrichloro-tin, diphenyldichloro-tin,phenylmethyldichloro-tin, phenylbutyldichloro-tin andphenylvinyldichloro-tin.

Among the alkenylchlorostannanes, there may be mentioned by way ofillustration, vinyltrichloro-tin, lpropenyl-trichloro-tin,l-butenyl-trichloro-tin, divinyldichloro-tin, vinylbutyldichloro-tin,vinylmethyldichloro-tin, vinylphenyldichloro-tin and the like.

Alkenylchlorostannanes, and in particular vinylchlorostannanes, areimportant intermediates in synthesis in organometallic chemistry. Theymake it possible to gain access to compounds which have diverseindustrial applications, particularly in the field of fungicides and inthe field of stabilisers for plastics. Organo-tin 'vinylmercaptides andvinyl maleates may be mentioned in this context.

Organochlorostannanes containing aromatic groups directly bonded to thetin atom, and in particular phenylchlorostannanes, make it possible togain access to compounds which have diverse industrial applicationsamongst which the preparation of fungicides and stabilisers may bementioned.

The examples which follow illustrate the invention.

Example 1 130 g. of stannic chloride and 7 g. of ground aluminiumchloride are introduced into a flask and then 75 g. oftrimethylphenylsilane are run in over the course of 1 hour at ambienttemperature (20 C.), followed by 6.1 g. of acetone. On rectification ofthe mixture, g. of phenyltrichlorostannane are obtained (Boiling point110-114 C.) (yield: 79.5%).

Example 2 100.7 g. of trichlorophenylstannane and 5.1 g. of aluminiumchloride are introduced into a flask, and 50 g. of trimethylphenylsilaneare run in over the course of 1 hour at 20 C. After adding 4.4 g. ofacetone and distilling, diphenyldichlorostannane is obtained in a yieldof 25%.

Example 3 127 g. of diphenyldichlorosilane, g. of stannic chloride and9.7 g. of aluminium chloride are introduced into a reactor flask and themixture is heated at 100 C. for 2 hours. After cooling to ambienttemperature, 7.6 g. of acetone are added and, on distillation,phenyltrichlorostannane is obtained in a yield of 66.1%.

Example 4 The reaction mixture consisting of:

G. Trichlorophenylstannane 60.4 Diphenyldichlorosilane 50.6 Aluminiumchloride 3.8

is heated at 200 C. for 2 hours.

After cooling to ambient temperature, 3.3 g. of acetone I are added and,after distillation, diphenyldichlorostannane is isolated in a yield of34.4%.

Example 5 260.7 g. of stannic chloride, 100 g. of trimethylvinylsilaneand 1.5 g. of ground aluminum chloride are introduced into a flask.Following a method of working identical to that of Example 1, 101 g. oftrimethylchlorosilane and 191.5 g. of vinyltrichlorostannane (Boilingpoint 55-60 C.) are isolated after rectification.

Example 7 The following amounts of reagents are introduced into areactor flask:

G. Stannic chloride 130.5 Trimethylvinylsilane Aluminium chloride 2Following the method of working of the preceding experiments, 144.5 g.of trimethylchlorosilane and 106 g. of

divinyldichlorostannane (Boiling point 76-80 C.) are isolated afterrectification.

Example 8 120 g. of methyltrichlorostannane, 53 g. oftrimethylvinylsilane and 1 g. of aluminium chloride are introduced inwhich R represents a chlorine atom or an alkyl radical with 1 to 4carbon atoms and wherein n is O, 1 or 2, or a group Z having the generalformula:

in which R R and R which may be identical or different, each represent ahydrogen atom or a saturated or unsaturated aliphatic, cycloaliphatic oraromatic hydrocarbon radical, or two radicals R and R together with thetwo ethylenic carbons to which they are bonded, form an unsaturated ringhaving 5 or 6 carbon atoms in the ring, in which a tin halide of thegeneral formula:

is reacted in the presence of aluminium chloride, with an organosiliconcompound of the formula:

CH3) [44mm III wherein Y and Z are as defined above, a is 1, 2, 3 or 4,b is 0, 1, 2 or 3, the sum (a-l-b) is not greater than 4, b being 0 whenZ is Z 2. A process according to claim 1, wherein Y represents achlorine atom, a straight or branched, saturated or unsaturated,aliphatic hydrocarbon radical having at most 6 carbon atoms, acycloalkyl or cycloalkenyl radical having 4 to 6 carbon atoms in thering, or a phenyl,

alkylphenyl or phenylalkyl radical in which the alkyl group contains 1to 4 carbon atoms.

3. A process according to claim 1 wherein Z is Z n is 0 or 1 and Rrepresents a chlorine atom or a methyl radical.

4. A process according to claim 1 wherein Z is Z a is 1 and R R and Reach is a hydrogen atom, straight or branched, saturated or unsaturated,aliphatic hydrocarbon radical having at most 6 carbon atoms, acycloaliphatic or cyclolkenyl radical having 4 to 6 carbon atoms in thering, or a phenyl, alkylphenyl or phenylalkyl radical in which the alkylgroup contains 1 to 4 carbon atoms or R and R together with the twoethylenic carbons to which they are bonded, form an unsaturated ringwith 5 or 6 carbon atoms in the ring. 5. A process according to claim 1wherein the tin halide is stannic chloride, trichlorophenylstannane,butyltrichlorostannane or methyl trichlorostannane and the organosiliconcompound is trimethylphenylsilane, diphenyldichlorosilane ortrimethylvinylsilane. 6. A process according to claim 1 wherein thereaction is carried out in the liquid phase at 10250 C. 7. A processaccording to claim 1 wherein, at the end of the reaction, acetone isadded to the reaction mixture to complex the aluminium chloride.

References Cited UNITED STATES PATENTS 2,873,287 2/ 1959 Ramsden260429.7 2,873,288 2/1959 Rosenberg et al. 260429.7 3,027,393 3/1962Jenkner et a1 260429.7 3,287,386 11/1966 Neumann 260429.7 3,752,8358/1973 Shapiro 260429.7 3,754,012 8/ 1973 Bulten 260429.7

OTHER REFERENCES Connor et al., Chemical Abstracts, 65 (1966), column8945d.

DANIEL E. WYMAN, Primary Examiner A. P. DEMERS, Assistant Examiner US.Cl. X.R. 260448.2 E

1. A PROCESS FOR THE PRODUCTION OF A CHLOROSTANNANE HAVING THE GENERALFORMULA: